Vat dyestuffs



Patented May 12, 1931 sr'rs UNITE MAX ALBERT KUNZ, 0F IIANNHEIM, AND KARL KOEBERLE, OF 'LUDWIGSHAFEN-ON- THE-RHINE, GERMANY, ASSEGNORS T0 GENERAL ANILENE' W'ORKS, INCL, OF NEW YORK, N. Y, A CORPORATION OF DELAWARE i i VAT DYESTUFFS No Drawing. Application filed. Beceinber 14, 1929, $eria1 No. 414,244,, and in Germany December 15, 1928.

The present invention relates to the manufacture and production of vat dyestuffs.

We have found that vat'dyestuifs having very varied shades and properties, and which in many cases may be employed as intermediates for the manufactureof other vat dyestufis are obtained bytreating with condensing agents having a reducing action '1.1-dianthraquinonyls of the following general formula:

H ll t H o t 9/ in which X and Y may be hydrogen or halogen, the oxygen atoms in the 9 and 9' positions and the hydrogen atoms in the Band positions may beireplaced by linkages connecting the said positions with each other and in which theanthraquinonyl radicles may be substituted. v By the termcondensing agents having a reducing action we intend densingagents to which reducing agents have been added, as Well as compounds as by themselves act as condensing and reducing agents simultaneously. As acid condensing agents there may be employed sulphuric acid or derivatives thereof, such as forexample ioleum or chlorosuphonic acid'to which reducing agents have been added as which may be mentioned metals, for instance copper, aluminium, zinc and the like, or reducing compounds thereof, such as 'cuprous oxide,

cuprou's halides, or metal sulphides. Alkaline agents which may be made use of are for example solutions of the hydroxides of alkali metals or alkaline earth metals or alkaline compounds of the said metals,such as 3 carbonates, acetates and the like, to which reducing agents, such as for example alkali metal hydrosulphite, hydrazine, hydroxylamine, alkali metal or alkaline earth metal sulphides have been added Condensing agents which at the'same time have a reducv products are obtained, namely for example,

from omega-omega-tetrabrom-2.2 dimethyl- 1.1-dianthraquinonyl 2.2-e thylene-l.1-dianthraquinonyl, allo ms naphthodianthrone and ms-anthradianthrone. The reactions proceed somewhat as shown in the following diagram: 1

Omega-omega'-tetrabromo-2.2'-dimethyl- 1.1-dianthraquinony1 alloms-naphthodianthrone ms-anthradianthrone dlanthraquinonyl Generally speaking, the saidproducts are produced simultaneously though in different absence of any solvent.

amounts according to the working conditions which however may be varied so as to obtain one of the aforesaid products as the main or even as the sole product. For example 2.2- et-hylene-1.1-dianthraquinonyl is obtained as the main product in the reduction of omega omegatetrabromo 2.2 dimethyl- 1.l-dianthraquinonyl with weak alkaline reducing agents as for example sodium hydrosulphite in alkaline solution, while allo- -ms-naphthodian.throne is formed in a yield of more than 90 per cent of the theoretical yield by reduction in acid media at low temperatures, i. e..below about 50 C. Alloms-n'aphthodianthrone is also obtained as the main or even exclusive product when treating initial materials in which the 9.9- positionsare linked together, i. e. from omega-omegatetrahailogen-22- dimethyl msbenzdianthrone by means of alkaline condensing agents having a reducing action at any temperature; Anthradianthrone is obtained as main product by first treating omega-omegatetrahalogen 2.2- dimethyl 1.1- dianthraquinonyl in acid media at low temperatures and then raising the temperature,

or from the said initial material in which the 9;9 -positions and the 8-8-positions are'linked together in alkaline media.

"The productsmay'further be subjected to halogenation according to' known methods, for example in organic solvents, water, sulphuric acid or derivatives thereof or in the The crude products may be purified or separated from theother compounds simultaneously formed, if desired, by the usual methods as for example by crystallization from organic solvents of high boiling point, or by way of their oxonium salts or by treatment with organic solvents or alkalies or with oxidizing ,agents,'for example by treatingthe aqueous pastes with sodium hypochlorite.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples. The parts are by weight.

" Example 1 400. parts of pyridine, poured into 4000 parts of Water and are heated to from 7 0 to 80 Centigrade on the water bath after the addition of 500 parts of 40 per cent caustic soda solution and 150 parts of sodium hydrosulphite. A clear violet wine red solution is thus obtained. If necessary any impurities pres ent are filtered off by suction and the dyestufi' free from halogen which has been formed is precipitated by blowing in air, and the precipitate is filtered ofi by suction and dried. It is a yellow orange powder which dissolves in concentrated sulphuric acid giving an olive green coloration and gives a violet wine red vat from which cotton is dyed yellow orange shades. By purification, for example by extraction with pyridine, pure 2.2-ethylene- 1.1-dianthraquinonyl is obtained which crystallizes in yellow needles which melt at about 345 C. with decomposition, and which dissolves in concentrated sulphuric acid giving an olive brown coloration and dyes cotton orange yellow shades from an orange' red vat.

7 Example 2 V 760 parts of omega-omega-tetrabromo- 2.2-dimethyl-1.1'-dianthraquinonyl are suspended at about 0 C. in 7600 parts of concentrated sulphuric acid whilestir'ring. 500 parts of copper power are'added, the whole is kept at low temperature for several hours and then, if necessary, the whole is warmed for an hour at from 40 to 50 C. The green reaction liquid is freed from unchanged copper by filtration by suction, is poured into ice water and the precipitate is filtered off by suction and dried. The dyestufi thus obtained in a quantitative yield is identical with the allo-ms-naphthodianthrone obtained according to Example 1 of the application Ser. No. 199,420. It is an orange red powder, comparatively readily soluble in organic solvents of sigh boiling point and crystallizes therefrom in prismatic orange red needles which melt at about 350 C. The solution of the product in concentrated sulphuric acid is emerald green in color .andshows a characteristic absorption line in the green region of the spectrum. It yields orange dyein-gs of very good fastness to washing and chlorine'on vegetable fibres from a red violet vat.

Instead of copper, other metals as for example aluminium bronze or zinc dust, or other reducing agents such as hydrazine hy drate and the like may be employed.

Emampl 3 100 parts of tetrabromo-2.2-dimethyl-msbenzdianth-rone, containing the bromine in v part in the nucleus, obtainable by brominating 2.2-dimethyl-ms-benzdianthrone in nitrobenzene at between 160 and 170 (1. are

boiled, while stirring, in 2000 parts of pyridine until a sample furnishes a violet vat. The reaction mixture is then allowed to cool and the reaction product filtered oif. The bromo-allo-ms-naphthodianthrone obtained in the form of copper-red needles dissolves in concentrated sulphuric acid to give a green solution and dyes cotton strong brilliant red shades from a violet vat.

Emample 4 83 parts of 4. 1-dichloro-omega-omegatetrabromo -2.2 dimethyl-1.1-dianthraquinonylobtainable by brominating 42.4:"dlChlOI'O- 2.2dimethyl-1.1-dianthraquinonyl in nitrobenzene at between 160 and 180 C. are suspended at about C. in 1000 parts of concentrated sulphuric acid. 80 parts of copper chips are then introduced into the reaction mixture which is stirred for several hours at between 5 and C. and then allowed to warm to about C. at which the reaction mixture is kept until it has a pure green coloration. The reaction mixture. is then worked up as described in Example 2. The reaction product, 4.4--dichloro-allo-ms-naphthodianthrone is an orange powder furnishing on cotton orange dyeings from a violet vat.

Ewample 5 70 parts of omega-omega-tetrachloro-2.2- dimethyl-ms-naphthodianthrone obtainable by chlorinating 2.2-dimethyl-ms-naphthodianthrone in boiling trichlorobenzene are introduced at between 120 and 130 G. into a melt of 200 parts of caustic potash and 200 parts of ethyl alcohol, while stirring, the reaction mixture being then heated to 180 C. and kept thereat until a sample furnishes in which X and Y may be hydrogen or halogen, the oxygen atoms in the 9 and 9 positions and the hydrogen atoms in the 8 and 8' positions may-be replaced by linkages connecting the said positionswith each other and in which the anthraquinonyl radicles maybe substituted. I

2. A process for the manufacture of vat dyestuffs which comprises treating with an alkaline condensing agent having a reducing action 1.1-dia-nthraquinonyls of the general formula; 1

Hal 9 x 5% Y H O H C") X if.

in which X andY may be hydrogen or halogen, the oxygen atoms in the 9 and 9 positions and the hydrogen atoms in the 8 and 8 positions may be replaced by linkages connecting the said positions with each other and in which the anthraquinonyl radicles may be substituted. s

4. A- process for the manufacture of vat dyestuffs which comprises treating with a weak alkaline condensing agent having a reducing action an omega-omega-tetrahalogen 2.2 dimethyl 1.1 dianthraquinonyl.

5. A process for the manufacture of 2.2- ethylene-l.1-dianthraquinonyl which comprises treating with pyridine omega-omegatetrabromo -22 dimethyl 1.1 dianthraquinonyl.

4- 6, As new article of manufacture 2:2,- ethylene-l.ldianthraquinony1 forming an orange powder dissolving in cqncentrated sulphuric acid to give an olive-,g*reen colorati-on and dyeing cotton from aviolet Wine red vat yellow orange shades.

In testimony whereof set our hands.

MAX ALBERT KUNZ. KARL KOEBERLE.

we have hereunto CERTIFICATE OF connection.

Patent No. 1,804,535. Granted May 12, 1931, to

MAX ALBERT KUNZ ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, line 89, for the word "power" read powder; page 3, in the formula of claiml, line 60, for "Ba" read Hal; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 4th day of August, A. D. 1931.

- Wm. A. Kinnan, (Seal) Acting Commissioner of Patents. 

